Stable compositions comprising benzoyl peroxide and low viscosity, lipophilic solvents and methods and systems related thereto

ABSTRACT

Compositions, methods, etc., directed to the stable delivery of benzoyl peroxide (BPO) or other suitable oxidizers into difficult substrates using low viscosity, lipophilic solvents, such as for stain removal or modification. For example, the compositions, methods, etc., can be used to remove autofluorescent organic stains such as pink stains caused by  Streptoverticillium reticulum  in marine vinyl or any other suitable substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of co-pending U.S. Provisional Patent Application Ser. No. 62/137,597, filed Mar. 24, 2015; U.S. provisional patent application No. 62/196,867, filed Jul. 24, 2015; and, U.S. provisional patent application No. 62/196,862, filed Jul. 24, 2015, which applications are incorporated herein by reference in their entirety.

BACKGROUND

A common issue in marine environments is a pink stain (pink-stain) apparently produced by Streptoverticillium reticulum as a byproduct of its metabolic processes, which stain appears to be comprised of an organic colorant. This organic colorant is soluble in polyvinylchloride (PVC) and other synthetic or natural materials. The S. reticulum stain (as well as other pink-stains comprising organic pigments or organic dyes created by microorganisms such as bacteria of the order Actinomycetales or the family Streptomycetaceae) appears on white marine vinyl and is a long-standing, prevailing problem in the pleasure and commercial boating industry for decades, well over 30 years. Accordingly, this is a long standing issue of great concern to vinyl manufacturers and users, as well as other manufacturers of other materials wherein such organic stains are problematic.

Thus, there has gone unmet a need for improved compositions, devices, systems, methods, etc., that remove such pink-stains. The present systems and methods, etc., provide these and/or other advantages.

SUMMARY

The compositions, methods, etc., herein are directed to compositions for the stable delivery of benzoyl peroxide (BPO) or other suitable oxidizers, such as those mentioned in U.S. patent application Ser. No. ______, filed contemporaneously herewith on Mar. 24, 2016 and entitled COMPOSITIONS, DEVICES, SYSTEMS AND METHODS RELATING TO PHOTO- AND THERMAL-OXIDATIVE BLEACHING OF PINK-STAINS (incorporated herein by reference in its entirety; serial number may be entered after filing) using low viscosity, lipophilic solvents, such as for stain removal or modification. For example, the compositions, methods, etc., can be used to remove autofluorescent organic stains such as pink stains caused by Streptoverticillium reticulum in marine vinyl or any other suitable substrate.

In one aspect the discussion herein can be directed to compositions comprising an oxidizing agent carried in an organic solvent having a polarity of about 2 to 3, a viscosity of about 0.3 cP to 1.0 cP, and a vapor pressure of 15 to 250 mm Hg, wherein a coating of the organic solvent applied to a marine vinyl fabric with a fine brush can fully evaporate at the surface within at least about 10 seconds at a temperature of 20° C., wherein the oxidizing agent can comprise peroxide, benzoyl peroxide, ozone, percarbonate, perphosophate or hydrogen peroxide. In some embodiments, the organic solvent when applied to a marine vinyl fabric with a fine brush can fully evaporate at the surface within at least about 10 seconds to 60 seconds at a temperature of 20° C. The organic solvent can have a polarity of about 2.5; a viscosity of about 0.7 cP to 0.9 cP, or about 0.8 cP; and a viscosity of about 0.8 cP.

The organic solvent can comprise a benzene ring and can comprise one or more of xylene, toluene, methyl ethyl ketone (MEK) or methyl tertiary butyl ether (MTBE). The composition can also comprise one or more of a peroxide, benzoyl peroxide, ozone, bleach (sodium hypochlorite), hydrogen peroxide. The composition can consist essentially of the oxidizing agent and the organic solvent, for example benzoyl peroxide in xylene. Such compositions can consist essentially of about 3% to 25% oxidizer, e.g., benzoyl peroxide, in a corresponding 97%-75% solvent, e.g., xylene (w/w); 10% to 15% oxidizer, e.g., benzoyl peroxide, in a corresponding 90%-85% solvent, e.g., xylene (w/w); or, about 11% oxidizer, e.g., benzoyl peroxide in 89% solvent, e.g., xylene (w/w).

The aspects and embodiments herein also include methods of making and using the compositions herein, as well as kits, containers, composition-specific labels and other items containing or relating to the compositions herein.

The aspects and embodiments herein also include treating autofluorescent organic stains of microorganism origin, as well as systems and kits configured to implement the methods herein, and methods of making such systems.

These and other aspects, features and embodiments are set forth within this application, including the following Detailed Description and attached drawings. Unless expressly stated otherwise, all embodiments, aspects, features, etc., can be mixed and matched, combined and permuted in any desired manner In addition, various references are set forth herein, including in the Cross-Reference To Related Applications, that discuss certain systems, apparatus, methods and other information; all such references are incorporated herein by reference in their entirety and for all their teachings and disclosures, regardless of where the references may appear in this application.

DETAILED DESCRIPTION

The systems, methods. etc., herein improve pink-stain removal from a substrate using strong oxidizing agents such as peroxides, or organic or oxygen radicals, such as benzoyl peroxide, ozone, hypochlorite (bleach), percarbonates, perphosophates or hydrogen peroxide.

One embodiment of the compositions, methods, etc., herein is to provide compositions comprising effective solvents such as xylene to deliver strong oxidizing agents such as BPO. Such compositions can be used to reduce and/or render invisible such stains in marine vinyl upholstery and other substrates, including the removal of pink colored stains in marine vinyl fabric caused by S. reticulum bacteria.

The stains discussed herein can be eliminated using strong oxidizing agents such as peroxides, or organic or oxygen radicals such as BPO, ozone, percarbonates, perphosophates or hydrogen peroxide carried by the solvents discussed herein.

Turning to a further discussion of the current compositions, methods, etc., herein, in some embodiments such compositions comprise a solvent that is characterized, for example, by being an organic solvent having a polarity of about 2 to 3, typically about 2.5; a viscosity of about 0.2 cP or 0.3 cP to 1.0 cP or 1.5 cP, or about 0.7 cP to 0.9 cP, or about 0.8 cP; and a vapor pressure of 15 to 250 mm Hg, such that a coating of the solvent applied to a marine vinyl fabric with a fine brush will fully evaporate within about 10 seconds at an ambient temperature of 20° C.; such a solvent may have a benzene ring, such as xylene, in combination with BPO or other suitable oxidizer.

The compositions, etc., herein comprise in one example a solution of BPO, a chemically active ingredient, in xylene, the solvent. BPO is stable when dissolved in xylene; a solution of 10% BPO (w/w) can be achieved at standard conditions (per National Institute of Standards and Technology (NIST), standard conditions are 20° Celsius and 101,325 Pa (1 atm)). This combination of xylene and BPO results in stability of the BPO, absence of damage to substrates that may contain S. reticulum stain such as PVC, absence of significant damage to vinyl finish, and low viscosity. Significant damage to vinyl fabric as the result of stain removal treatment to the treated area includes, for example, discoloration detectable by the human eye, removal of water proofing, accelerated aging, reduction in shear or tear strength, physical deformation, increased Shore Durometer hardness (durometer is one of several measures of the hardness of a material. Hardness can be defined as a material's resistance to permanent indentation as defined by Rockwell Corporation Shore Durometer calibrated measuring devices. ASTM D2240. Standard Test Method for Rubber Property), reduced ASTM D2240 elastic modulus, or changing how the treated fabric feels to the touch.

Suitable xylene or other suitable organic solvent concentrations can be about 75%, 80%, 85%, 90%, 95% or 97% (w/w).

The current solutions, compositions, methods, etc., can also remove pink-stain and other autofluorescent organic stains at depth in a substrate such as marine vinyl. For example, in some embodiments, the pink-stain can be removed not just from the visible surface but also as much as about 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 07 mm, 0.8 mm, 0.9 mm, 1.0 mm or 1.1 mm deep, or more, in an affected area of vinyl upholstery. Thus, for a 1.1 mm, 1.2 mm, 1.5, mm, etc., thick piece of upholstery, the compositions, methods, etc., herein can remove pink-stain all the way through the upholstery. Substrates herein can also include rice, wheat flour, etc.

Significant economic value can be realized with predictable, complete eradication of pinking on boat vinyl fabric. Eradication of stains via these methods represent a significant reduction in cost and time when compared to replacing stain-damaged vinyl fabric.

The solvent compositions, etc., herein can improve both efficacy and time needed to complete successful treatment, for example compared to delivering BPO to vinyl fabric using an aquatic suspension of BPO particulates for superficial application. The compositions, etc., herein can improve upon the aquatic suspension method by dissolving BPO into xylene to provide a composition with low polarity and low viscosity so that it can enter small cracks and fissures in the surface of fabric easily, and sufficiently low vapor pressure so that it will evaporate rapidly once it has been applied to a stain under standard conditions (e.g., the composition will penetrate the vinyl and dry in less than about 20 seconds, 10 seconds, or 5 seconds, at 20° C. at 1 atmospheric pressure at sea level).

Significant amounts of BPO can go into solution in xylene, for example about 2% BPO, 3% BPO, 5% BPO, 8% BPO, 10% BPO, 11% BPO, or 12% BPO (w/w), and thus for an 11%BPO solution, about 0.05 milliliters of solution containing 730 micrograms of BPO per square inch of vinyl fabric. This combination of properties allows for a deeper and much more rapid delivery of BPO into the vinyl for pink-stain treatment compared to aqueous suspensions. With BPO dissolved in Xylene, the properties of the solvent are preserved, such as 2.5 polarity, 0.8 cP viscosity and 18 mmHg vapor pressure. Other exemplary organic solvents include toluene, methyl ethyl ketone and benzene.

In one embodiment for use of the compositions herein, the treatment of pink-stains, the solution was applied with a fine painter's brush or felt pen. The solution penetrates cracks and fissures of the vinyl fabric and carried amounts of BPO with it that were sufficient for complete pink-stain eradication. The low vapor pressure of xylene means that it will evaporate quickly. As it evaporates, BPO comes out of solution as very fine crystals. Such fine crystals, having large surface area for their volume, will readily penetrate into the vinyl fabric everywhere the xylene or other suitable solvent carries them. In other words, BPO was carried into vinyl fabric everywhere the solvent was able to reach.

In some other embodiments, the compositions comprise other solvents able to dissolve benzoyl peroxide. Exemplary properties of suitable solvents include the following:

-   -   Dissolves benzoyl peroxide to form a solution of benzoyl         peroxide adequate to treat the pink-stain, for example about 8%         to 12% BPO (w/w).     -   Forms a stable solution that does not substantially degrade BPO,         is free from secondary reactions such as the formation of         explosive peroxides, and maintains those qualities for a minimum         of six months when stored at temperatures less than 113 degrees         F.     -   The solution has low viscosity to enter fissures and cracks in         vinyl fabric.     -   The dried solution's residue does not auto ignite at or below         160° F. in air.     -   The solution does not alter or otherwise damage the vinyl         fabric.     -   The solution does not alter or damage any non-vinyl coating on         the fabric, such as acrylic coatings.     -   The solution, once applied, will evaporate within seconds.     -   The solvent having a polarity of about 2.5; a viscosity of 0.8         cP or less.     -   The solvent having a vapor pressure of 15 to 250 mm Hg.     -   The solvent may have a benzene ring in chemical composition.

Some exemplary alternate solvents include toluene, methyl tertiary butyl ether (MTBE) and methyl ethyl ketone (MEK).

Further embodiments for forming a solution of benzoyl peroxide in a suitable solvent include:

-   -   Use of solvent other than xylene     -   Direct formation of desired concentration of benzoyl peroxide in         solution using sufficiently pure ingredients to eliminate the         filtration step.     -   Agents to increase viscosity such as Carbomer copolymers type         940 and Homopolymer type A, B, or C.     -   Agents to control odor

Other compositions include colloidal suspensions of BPO (or other oxidizer) dissolved in a solvent mixed in an immiscible carrier, or colloidal suspensions of solid BPO in a suitable carrier.

An exemplary protocol comprises:

-   -   1. Provide a S. reticulum pink-stained piece of fabric.     -   2. If desired, perform a fluoroscopic analysis of the stained         fabric such as vinyl; take still picture if desired for later         comparison.     -   3. Apply BPO in xylene solution with painter's brush to the         stained fabric.     -   4. Let dry about 15 seconds.     -   5. Apply light and heat to illuminate at 492 nm with 2 W/square         inch at a surface temperature of 150° F. Apply for 10 minutes.     -   6. Repeat steps 2 to 4 one to three times (i.e., reapply the         BPO-xylene solution and light/heat two times), typically two         times, as needed to eliminate the pink-stain visible to the         human eye.     -   7. If desired, perform a further analysis capable of determining         the presence of the pink-stain below the surface of the fabric,         for example a fluoroscopic analysis. If desired, take still         picture to document the status and/or elimination of the         pink-stain.

Example 1 Elimination of Pink Organic Stains Using BPO in Xylene

BPO powder, consisting of 75% benzoyl peroxide and 25% water, was added to 100% xylene. The mixture was heated to 100° F. and shaken continuously until the BPO powder was dissolved. More powder was added until a saturated solution of benzoyl peroxide in xylene was formed. The approximate concentration was 11% benzoyl peroxide (w/w). This resulted in a turbid mixture, which was then filtered through a 20 micron paper filter. The filtrate was let stand for about 20 minutes for water to settle out.

The filtration process was stopped when about 80% of the initial mixture had passed through the filter. The remainder, consisting of water, suspended water, xylene, and BPO powder and solution, was discarded. This procedure was carried out using closed vessels for mixing, then used a filter open to the air, and was at 20° C. and atmospheric pressure. The solution, once created, was held in a closed glass vessel.

A solution of benzoyl peroxide of 11% (w/w) was formed. This solution was clear and colorless.

A clean artist's oil paint brush of approximate ⅜″ width was used to apply the solution to vinyl fabric affected by pink-staining. Once the brushed area was visibly dry, a combination heat and light source are placed directly overhead. The light source had a luminous output of about 1.8 W per square inch of light at a wavelength of 492 nm, and the temperature on the vinyl was raised to and held at 150° F. for a period of ten minutes. The application of the solution to the stained vinyl and subsequent illumination and heating were repeated three times. Fluoroscopic examination showed complete eradication of pinking at the end of this process.

Example 2 Elimination of Pink Organic Stains from Bacteria S. Reticulum with Increased Temperature

1) Apply a 10% (w/w) solution of BPO dissolved into xylene applied to a pink-stain on white marine vinyl.

2) The target area/stained substrate was heated to about 145° F. using a built-in heat source (max. about 150° F.).

3) Expose the pink-stained area for 10 min using 200 W (radiometric luminous energy 50 W) over an area of 25 in², which is about 2 W/in² (3,000/m²), using a treatment wavelength band of 490-495 nm produced by two 100 W LED arrays, with a peak of 494 nm, ½ intensity bandwidth of 26 nm (Q-factor of 19.1).

Repeat steps 1-3 as desired to achieve removal to elimination of the pink-stain. In some embodiments, the steps are repeated 6 times.

All terms used herein are used in accordance with their ordinary meanings unless the context or definition clearly indicates otherwise. Also unless expressly indicated otherwise, in the specification the use of “or” includes “and” and vice-versa. Non-limiting terms are not to be construed as limiting unless expressly stated, or the context clearly indicates, otherwise (for example, “including,” “having,” and “comprising” typically indicate “including without limitation”). Singular forms, including in the claims, such as “a,” “an,” and “the” include the plural reference unless expressly stated, or the context clearly indicates, otherwise.

The scope of the present devices, systems and methods, etc., includes both means plus function and step plus function concepts. However, the claims are not to be interpreted as indicating a “means plus function” relationship unless the word “means” is specifically recited in a claim, and are to be interpreted as indicating a “means plus function” relationship where the word “means” is specifically recited in a claim. Similarly, the claims are not to be interpreted as indicating a “step plus function” relationship unless the word “step” is specifically recited in a claim, and are to be interpreted as indicating a “step plus function” relationship where the word “step” is specifically recited in a claim.

From the foregoing, it will be appreciated that, although specific embodiments have been discussed herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the discussion herein. Accordingly, the systems and methods, etc., include such modifications as well as all permutations and combinations of the subject matter set forth herein and are not limited except as by the appended claims or other claim having adequate support in the discussion and figures herein. 

1. A composition comprising an oxidizing agent carried in an organic solvent having a polarity of about 2 to 3, a viscosity of about 0.3 cP to 1.0 cP, and a vapor pressure of 15 to 250 mm Hg, wherein a coating of the organic solvent applied to a marine vinyl fabric with a fine brush will fully evaporate at the surface within at least about 10 seconds at a temperature of 20° C., wherein the oxidizing agent comprises peroxide, benzoyl peroxide, ozone, percarbonate, perphosophate or hydrogen peroxide.
 2. The composition of claim 1 wherein the organic solvent when applied to a marine vinyl fabric with a fine brush will fully evaporate at the surface within at least about 10 seconds to 60 seconds at a temperature of 20° C.
 3. The composition of claim 1 wherein the organic solvent has a polarity of about 2.5.
 4. The composition of claim 1 wherein the organic solvent has a viscosity of about 0.7 cP to 0.9 cP, or about 0.8 cP.
 5. The composition of claim 1 wherein the organic solvent has a viscosity of about 0.8 cP.
 6. The composition of claim 1 wherein the organic solvent comprises a benzene ring.
 7. The composition of claim 1 wherein the organic solvent comprises xylene.
 8. The composition of claim 1 wherein the organic solvent consists essentially of xylene.
 9. The composition of claim 1 wherein the organic solvent comprises toluene.
 10. The composition of claim 1 wherein the organic solvent consists essentially of toluene.
 11. The composition of claim 1 wherein the organic solvent comprises methyl ethyl ketone (MEK).
 12. The composition of claim 1 wherein the organic solvent consists essentially of methyl ethyl ketone (MEK).
 13. The composition of claim 1 wherein the organic solvent comprises methyl tertiary butyl ether (MTBE).
 14. The composition of claim 1 wherein the organic solvent consists essentially of methyl tertiary butyl ether (MTBE).
 15. The composition of claim 1 wherein the oxidizing agent comprises a peroxide.
 16. The composition of claim 1 wherein the oxidizing agent comprises benzoyl peroxide.
 17. The composition of claim 1 wherein the oxidizing agent comprises ozone.
 18. The composition of claim 1 wherein the oxidizing agent comprises hydrogen peroxide.
 19. The composition of claim 1 wherein the oxidizing agent comprises sodium hypochlorite.
 20. The composition of claim 1 wherein the composition consists essentially of the oxidizing agent and the organic solvent.
 21. The composition of claim 19 wherein the composition consists essentially of benzoyl peroxide in xylene.
 22. The composition of 21 wherein the composition consists essentially of about 3% to 25% benzoyl peroxide in about 97%-75% xylene (w/w).
 23. The composition of 21 wherein the composition consists essentially of about 10% to 15% benzoyl peroxide in about 90%-85% xylene (w/w).
 24. The composition of 21 wherein the composition consists essentially of about 11% benzoyl peroxide in about 89% xylene (w/w). 